Process of effecting cation exchange



Patented June 11, 1940 2,204,539

PROCESS OF EFFEOTING CATION EXCHANGE Hans Wassenegger, Dessau in Anhalt,and Karl Jaeger, Frankfort-on-the-Main-Hochst, Germany, assignors to I.G. Farbenindustrie Aktiengesellschaft, Frankfort on the Main, Germany NoDrawing. Application June 21, 1938, Serial -No. 214,934. In GermanyFebruary 1, 1936 7 Claims.

Our present invention relates to a process of effecting cation exchangein aqueous solutions by treating them with artificial resins.

More particularly it relates to the use of comthe temperature is keptfor about 10 hours at 90 C. A hard black resin is formed which is stableto water and of conchoidal fracture. This resin is washed with water andground to a suitpounds which have outstandingly good cationable size ofgrain. It adsorbs up to 5 per cent. of

exchanging properties. its own weight of CaO from a solution of calciumOur invention is based on the discovery that chloride. By regenerationwith an acid or a artificial resins of excellent cation-exchangingsolution of common salt this base-exchanging properties are obtainableif care is taken that body regains its original absorption capacity.

the end products contain nuclear sulfonic acid Example 2.-115 parts ofsulfuric acid monolo radicles in their molecule. When producing suchhydrate are introduced in the course of 1 hour compounds, we eitherstart from materials which at 90 C. into 94 parts of hydroxy benzene.Then already contain sulfonic acid radicles, such as, the mixture isstirred at this temperature until for instance, hydroxybenzene-,naphthalene-, the odor of phenol has disappeared. The mixacenaphtheneorphenanthrene-sulfonic acids or ture is .then added to 170 parts of waterand 15 we after-treat the artificial resins obtained in caused to reactwith 150 parts of formaldehyde the normal way with sulfonating agents.In the at about 90 to 100 C. After hardening at 90 C. first case, thesaid aromatic sulfonic acids should a dark resin is formed havingsimilar properties be easily condensed with aldehydes. For subseas thatdescribed in Example 1.

quent sulfonation of artificial resins free of sul- Example 3.-60 partsof naphthalene are 20 fonic groups, such products are chosen whichheated during 3 hours with 90 parts of sulfuric yield diflicultlysoluble or insoluble sulfonation acid (monohydrate) to 140 to 150 C.After products. Especially suitable are granulated cooling to 75 90parts of a formaldehyde solution artificial resins which have a largeinterior surof 30 per cent. strength are introduced and heat- 5 facewhich is maintained, for instance, by careing to 90 to 100 C. iscontinued for 20 hours. fully drying the jellies resulting after thecon- .The solid gelatinous reaction mass adsorbs after at o I grindingand washing with water per liter about We are aware that resins offormaldehyde, 10 parts of CaO from a spring-water with 25 ,synthetictanning agents, e. g. condensation prodhardness (German degrees).

ucts of cresyl sulfonic acid formaldehyde, and Example 4.110 parts of1.3-dihydroxybenzene 3o polyhydroxybenzenes have already been proposedare introduced into 500 parts of sulfuric acid for cation exchange. Butthese are mixed conmonohydrate, the mixture is slowly heated todensation products, meanwhile corresponding to 105 C. and kept at thistemperature for about 2 the present invention resins are used which arehours. Then it is introduced in 250 parts of a built up by an aldehydeand merely one further formaldehyde solution of 30 per cent. strength.35 component containing nuclear sulfonic groups. After heating to 100 C.for 15 hours, a rather Our base-exchanging bodies when compared solid,red, gelatinous resin is obtained which after with known products ofthis kind show an ingrinding and washing until 'free from sulfuriccreased capacity for cation exchange or more acid, is dried. It isuseful for adsorption of 40 rapid exchange or an easier regeneration,that cations and may bind from an ammoniacal 40 is to say, they requirea smaller excess of reagent copper solution containing 0.16 gram ofcopper for producing the reverse exchange. This re- Del 11 Pe Cent- PD aculated on its generation may be carried out by means of suitown weight.able acids and salt solutions without injuring the Example 5.-l00 partsof 1.2-dihydr0xybenzene activity. are sulfonated as described in Example4. The 45 This application is a continuation-in-part of reaction mixtureis then introduced while stirring our application Serial No. 123,150,filed January in 200 parts of a formaldehyde solution of 30 per 30,1937. cent. strength. After heating to 100 C. for about The followingexamples illustrate the invention 14 hours a black resin is obtainedwhich is ground without limiting it, the parts being by weight: andwashed with water until free from acid. It 50 Example 1.-175 parts ofl-hydroxybenzene-ladsorbs from an ammoniacal copper solution 16 sulfonicacid are heated together with 40 parts parts of copper per 100 parts ofresin. The reof a formaldehyde solution of 30 per cent. generationpreferably is carried out with warm strength for hour to about 105 C.Then sulfuric acid, whereat the concentration of the further parts offormaldehyde are added and sulfuric acid is thus adjusted that aftercooling 55 parts of a formaldehyde solution of per cent.

strength and kept at this temperature for hours. The formed resin isworked up as indicated in Example 5. It may be applied for exchangingcations.

Example 7 .-50 parts of a resin formed from. are

1.3-dihydroxybenzene and formaldehyde, heated together with 750 parts ofoleum (containing 65 per cent. of S03) for 2 hours on the water-bath.The reaction product is separated from the oleum in excess, slowlyintroduced into water and washed until acid. It is an exchanging bodyfor H-ions and takes up 5 per cent. of its own weight-of calcium(calculated as CaO) from the solution of a calcium salt.

Example 8.-62 parts of acenaphthene are heated during 4 hours togetherwith parts of sulfuric acid (monohydrate) to 115 to 120. After addingparts of water and filtering by suction the filtrate is reduced to 94parts by distillation. This solution of acenaphthene sulfonic acid ismixed with 60 parts of a solution of formaldehyde of 40 per cent.strength and heated to to during 20 hours. The gelatinous reaction massgrows solid and is ground after drying at about 80. One liter of theproduct swollen in water adsorbs about 20 parts of C20 fromaspring-water, of 25 hardness (German degrees), the material being usedas a neutral or a hydrogen exchanger.

It is obvious that our invention is not limited to the foregoingexamples or to the specific details given therein. Thus, for instance,other aldehydes may be used, such as acetaldehyde or furfuraldehyde. Onthe other hand, the specific features maintained in carrying out theresin formation may be varied in the known manner, I

' 3. The process free from the adhering r. the copper sulfate formedseparates in crystals care being only taken that this condensation isperformed to such adegree that water-insoluble resins containingsulfonic acid groups are formed.

Whatjwe claim is: g

1. The process of effecting cation-exchange in aqueous solutions whichcomprises bringing the solution in contact with a water-insoluble resinof an aldehyde and a member of the group consisting of hydroxybenzene,naphthalene, acenaphthene, and phenanthrene, containing nuclear sulfonicacid groups.

2. The processof efiecting cation-exchange in aqueous'solutions whichcomprises bringing the solution in contact with'a water-insoluble resinof an aldehyde and naphthalene, containing nuclear sulfonic acid groups.

of effecting cation-excha ge in aqueous solutions which comprisesbringing the solution in contact with a water-insoluble resin offormaldehyde and naphthalene, containing nuclear sulfonic acid groups.

4. The process of effecting cation-exchange in aqueous solutions whichcomprises bringing the solution in contact with'a water-insoluble resinof an aldehyde and acenaphthene, containing nuclear sulfonic. acidgroups. I 7

5. The process of efiecting cation-exchange in aqueous solutions whichcomprises bringing the solution in contactwith a water-insoluble resinof formaldehyde and acenaphthene, containing nuclear sulfonic acidgroups.

6. The process of effecting cation-exchange in aqueous solutions whichcomprises bringing the solution in contact with a water-insoluble resinof an aldehydeand phenanthrene, containing nuclear sulfonic acid groups.'7. The process of effecting cation-exchange in aqueous solutions whichcomprises bringing the solution in contact with a water=insoluble resinof formaldehyde and phenanthrene, containing nuclear sulfonic acidgroups.

HANS WASSENEGGER. KARL JAEGER.

